等规双氮杂环类聚合物电子传输材料的设计、合成及场效应性能研究

Recently, high-mobility polymeric electron-transporting materials have attracted intensive attention due to great application potential in organic field-effect transistors (OFET), integrated circuits, and so on. Nowadays this kind of materials mainly suffer from the challenge of low electron mobility. In this project, an effective regioregular dual-acceptor strategy is used to enable two asymmetric N-heterocycles to link together, thus developing a series of regioregular dual N-heterocyclic acceptors with enhanced backbone conjugation and electron affinity. Our primary interest is to develop a set of dual-acceptor type polymeric materials with high electron mobility by introducing these dual N-heterocyclic acceptors into polymeric backbone. High electron mobility can be readily achieved for these polymers because the structural regioregularity, backbone coplanarity, energy level, and aggregation structure of the polymers can be fine-tuned by manipulation of regioregularity and molecular structure of these dual N-heterocyclic acceptors. On the basis of single-crystal structure of the small molecular model compounds, some important information about main-chain structure and carrier transport behavior of the polymers will be investigated carefully. Furthermore, we are going to systematically study the effect of molecular structure and aggregate structure of the polymers on carrier transport performance; the observed results will be helpful for deeply understanding carrier transport mechanism of the polymers. Combining reasonable molecular design with device optimization, high-performance, air-satble OFET devices based on our developed electron-transporting polymers will be fabricated finally. Our research results will provide innovative design strategy and novel materials for the development of flexible organic optoelectronic devices in the future.

高迁移率聚合物电子传输材料在有机场效应管(OFET)和有机集成电路等领域中具有重要的应用前景，近年来备受关注。本项目针对该类材料面临的电子迁移率低的问题，运用“等规双受体策略”将两个结构不对称的氮杂环受体直接相连，合成系列共轭骨架更大、电子亲和力更强的等规双氮杂环受体，并用于开发系列高迁移率的双受体型聚合物电子传输材料。通过剪裁双受体单元的结构规整性和分子骨架，可以方便地调控聚合物的结构规整性、骨架共平面性、能级以及聚集态结构等参数，最终实现高的电子迁移率。结合小分子模型化合物的单晶结构，间接获取聚合物主链结构与载流子传输的相关信息，进一步研究聚合物分子结构、薄膜聚集态结构和载流子传输性能的内在关联，更深层次的认识载流子传输机制。通过合理的分子剪裁与器件优化，制备出高性能、空气稳定的电子传输型聚合物OFET器件，为今后构造柔性有机光电器件提供新材料和新方法。

有机/聚合物电子传输材料是构造柔性有机场效应晶体管（OFET）、近红外光晶体管、有机热电器件等有机光电子器件的关键功能材料，近年来获得广泛研究。本项目开发了系列平面性好、骨架共轭大的高性能有机/聚合物电子传输材料，表征了材料的结构与光电性能，总结了材料分子结构与其薄膜结表面形貌、薄膜聚集态结构以及载流子传输性能之间的构效关系，主要研究结果如下：1) 发展系列噻二唑杂环类聚合物电子传输材料，其吸收边带拓宽至1880 nm，光学带隙最低达0.66 eV，该类材料展现出平衡的双极性载流子传输性能；2) 采用高效p-型和n-型掺杂，实现对苯并双噻二唑类双极性聚合物的可控掺杂，方便地调节为p-型或n-型两种单极性传输模式；3) 构建系列新型的芳香二酮衍生的有机/聚合物电子传输材料，其薄膜OFET器件的电子迁移率高达1.01 cm2 V–1 s–1，有机单晶OFET器件的电子迁移率高达12 cm2 V–1 s–1以上；4) 拓展噻二唑类聚合物电子传输材料的应用领域，发现该材料可促进肿瘤低温光热治疗。已发表标注有本项目编号的SCI论文11篇，包括1篇Matter, 1篇Angew. Chem. Int. Edit., 1篇Adv. Funct. Mater., 2篇Macromolecules，5项中国发明专利。本项目的研究成果丰富了有机/聚合物电子传输材料的材料体系，为今后构造柔性有机光电器件提供新材料和新方法。

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